A Cope Rearrangement in the Reaction Catalyzed by Dimethylallyltryptophan Synthase?

作者:Luk Louis Y P; Qian Qj; Tanner Martin E*
来源:Journal of the American Chemical Society, 2011, 133(32): 12342-12345.
DOI:10.1021/ja2034969

摘要

The enzyme dimethylallyltryptophan synthase catalyzes the "normal" prenylation of Tip at C-4 in the first step of ergot alkaloid biosynthesis. The Lys174Ala mutant is found to produce a hexahydropyrroloindole alkaloid that is "reverse-prenylated" at C-3 as its major product. This is interpreted as evidence in support of a mechanism that involves an initial "reverse-prenylation" at C-3, followed by a Cope rearrangement and rearomatization.

  • 出版日期2011-8-17